The present invention relates to novel organosilicone compositions and, more particularly, to silicone compositions having a carboxyl functional group thereon.
While some carboxyl functional organosilicones are known, they are generally difficult and expensive to prepare and the commercial use thereof has therefore been limited. Heretofore, no convenient method for directly preparing polysiloxanes containing functional carboxylic acid groups is known and indirect routes for their preparation have generally been used, such as hydrosilylation of an unsaturated ester followed by hydrolysis, or alternatively, by hydrolysis of nitrile-containing silicone fluids. However, polysiloxanes containing one or more functional groups such as amino and diamino functional groups are well known and have been used in a variety of commercial applications, but none of such polysiloxanes also contain functional carboxyl groups or provide an amphoteric class of organosilicones. Accordingly, the development of a method for readily and more directly preparing polysiloxanes containing one or more functional carboxyl groups would be desirable and it would be particularly advantageous if such method employed readily available silicone materials such as amino or diamino functional polysiloxanes for preparing not only a variety of carboxyl functional polysiloxanes including an amphoteric class of capped or uncapped organosiloxanes and organosilicone derivatives thereof as well.
While, as indicated, certain polysiloxanes containing functional carboxylic acid groups and methods for preparing the same have heretofore been suggested, there is no disclosure or suggestion of the novel carboxyl functional silicone compositions or the method of preparing the same described in commonly assigned U.S. Pat. Nos. 5,596,061; 5,807,955 and 6,100,358, whose contents are incorporated by reference herein.
It is accordingly an object of the present invention to provide a method for directly and readily preparing organosilicone compositions having at least one pyrrolidone-containing carboxyl functional group thereon and particularly an amphoteric class of organosilicone compositions.
It is still a further object of the present invention to provide a method of using cosmetic and personal care preparations which include novel carboxyl functional polysiloxane compositions, including an amphoteric class of polysiloxane compositions.
In accordance with the present invention, there has now been discovered novel capped or uncapped polysiloxanes containing one or more carboxylic acid groups and/or the ester derivatives thereof that may be represented by the following general formula: 
wherein: R1, which can be the same or different, can be selected from R2, an amine or a diamine containing group of the formula xe2x80x94F1xe2x80x94Bn2xe2x80x94Fxe2x80x94NH2, an oxygen containing group of the formula xe2x80x94OR11, wherein R11 is hydrogen or a lower alkyl (C1-6), and a pyrrolidone containing carboxyl functional group of the formula: 
wherein at least one of R1 is a pyrrolidone containing carboxyl or ester functional group or salt derivative thereof as shown; F1 is linear or branched alkylene of 1-12 carbon atoms, preferably a linear or branched alkylene of 1-4 carbon atoms; F is linear or branched alkylene of 1-10 carbon atoms, preferably ethylene; R2 is as defined below; R5 can be hydrogen, lower alkyl (C1-6) or alkali metal; and B is xe2x80x94NR9, wherein R9 is hydrogen or lower alkyl (C1-6) and further wherein n2 is 0 or 1;
R2 can be the same or different and can be selected from alkyl, aryl and olefinic (vinyl);
R3 and R4, which may be the same or different, are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and alkenyl (vinyl);
a can be an integer from 0 to 50,000; and
b can be an integer from 0 to 100.
In another aspect of the present invention uncapped polysiloxanes containing one or more carboxylic acid groups and/or the ester derivatives thereof are provided. For such uncapped polysiloxane compositions at least one R1 is an oxygen containing group of the formula xe2x80x94OR1, wherein R11 is hydrogen or a lower alkyl (C1-6).
In a further aspect of the present invention there is provided a method for preparing polysiloxanes containing one or more pyrrolidone-containing functional carboxylic acid groups and/or the ester derivatives thereof, and particularly an amphoteric class of polysiloxane compositions, which comprises reacting an organosilicone fluid or composition having at least one diamine functional group which must contain at least one primary amine group with itaconic acid or an ester derivative thereof at an elevated temperature (preferably from about 90xc2x0 C. to about 130xc2x0 C.) for a time sufficient to react, preferably substantially completely react (generally ranging from about 1-5 hours), the itaconic acid or ester thereof with the functional primary amine group(s) on the silicone fluid or composition to form an organosilicone composition having at least one pyrrolidone-containing carboxyl functional group.
In a still further aspect of the present invention there is provided a novel silicone-modified amidoamine composition having the formula: 
wherein: R10 is the silicone backbone chain as herein described to which at least one pyrrolidone containing amidoamine derivative of a pyrrolidone-containing carboxyl functional group can be attached as shown;
R6 is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each, cycloalkyl of up to 6 carbon atoms, or polyoxyalkylene of up to 10 carbon atoms within the oxyalkylene unit;
R7 and R8, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl; and polyoxyalkylene of up to 10 carbon atoms; in addition R7 and R9 taken together with the nitrogen to which they are attached may represent an N-heterocycle;
n3 is an integer and is at least 1, preferably an integer from 2 to 12;
n2 is 0 or 1 and B is xe2x80x94NR9, wherein R9 is hydrogen or lower alkyl (C1-6);
F1 is branched or linear alkylene of 1-12 carbon atoms;
F is branched or linear alkylene of 1-10 carbon atoms; and
d is at least one.
In a still further aspect of the present invention there is provided cosmetic and personal care preparations which contain at least 0.1%, preferably from 0.1% to 10%, of novel polysiloxanes containing one or more pyrrolidone-containing functional carboxyl groups and/or the ester or amidoamine derivatives thereof.
In accordance with the present invention there are provided novel capped or uncapped polysiloxanes comprising a class of carboxyl functional polysiloxanes including an amphoteric class of such polysiloxanes which may be represented by the general formula: 
wherein: R1, which can be the same or different, can be selected from R2, an amine or a diamine group of the formula xe2x80x94F1xe2x80x94Bn2xe2x80x94Fxe2x80x94NH2, an oxygen containing group of the formula OR11, wherein R11 is hydrogen or lower alkyl (C1-6), and a pyrrolidone containing carboxyl functional group of the general formula: 
wherein at least one R1 is a pyrrolidone-containing carboxyl or ester functional group or salt derivative thereof as shown; F1 is linear or branched alkylene of 1-12 carbon atoms, preferably a linear or branched alkylene of 1-4 carbon atoms including methylene, propylene and isobutylene ; F is linear or branched alkylene of 1-10 carbon atoms, preferably ethylene and isopropylene; R2 is as defined below; R5 is hydrogen, alkyl, preferably lower alkyl (C1-6), or an alkali metal; and B is xe2x80x94NR9, wherein R9 is hydrogen or lower alkyl (C1-6) and further wherein n2 is 0 or 1;
R2 can be the same or different and can be selected from alkyl, aryl and olefinic (vinyl);
R3 and R4, which may be the same or are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and alkenyl (vinyl);
a can be an integer from 0 to 50,000; and
b can be an integer from 0 to 100;
It is evident from the general formula above that the polysiloxane compositions of the present invention have one or more pyrrolidone-containing functional carboxyl or ester group(s) or salt derivative thereof linked terminally, laterally or both terminally and laterally to the silicone (polysiloxane) chain through a hydrocarbon linkage which contains at least one nitrogen atom.
Useful polysiloxanes include uncapped polysiloxanes containing one or more carboxylic acid groups and/or the ester derivatives thereof. For such uncapped polysiloxane compositions at least one R1 is an oxygen containing group of the formula xe2x80x94OR11, wherein R11 is hydrogen or a lower alkyl (C1-6).
The polysiloxane compositions including the amphoteric class of polysiloxanes according to the present invention are useful, for example, for reducing the friction of petroleum flow through pipelines and as additives for personal care products as well as being precursors for a wide range of personal care products, fiber treating agents and the like which impart such advantages as improved feel, substantivity, reduced surface tension, and anti-stick characteristics.
The novel functional carboxyl polysiloxanes and particularly the amphoteric class of polysiloxanes of the present invention surprisingly and unexpectedly can be readily and directly prepared by the reaction of corresponding silicone compositions or fluids having one or more functional diamine groups, each of which group(s) must contain a primary amine group, with up to about one equivalent, preferably about stoichiometric quantities, of itaconic acid or its ester per primary amine group portion of the functional diamine group(s) at an elevated temperature for the time sufficient for substantially all of the itaconic acid or its ester to react with the functional primary amine group(s). In general from about 0.5, preferably, from about 0.9 to about 1.1 equivalents of itaconic acid or its ester per functional primary amine group is reacted with the silicone fluid wherein substantially all the itaconic acid and preferably all the functional primary amine group(s) is reacted and a polysiloxane composition with at least one pyrrolidone-containing functional carboxyl group(s) and/or its ester or salt is formed.
The reaction can be carried out neat or in an inert solvent such as alcohol, hydrocarbon solvent, chlorinated hydrocarbon and the like, as desired, in general, at elevated temperature up to 175xc2x0 C., preferably from about 90xc2x0 C. to about 130xc2x0 C. The reaction readily proceeds and generally complete reaction of the itaconic acid or its ester with the available functional primary amine groups and cyclization to form a pyrrolidone group will occur in from about 1 to 5 hours. Routine analytical techniques for amine and acid values as well as monitoring viscosity, color and water and/or alcohol evolution can be used to determine completion of the reaction.
Suitable functional diamine silicone fluids for use in accordance with the practice of the invention, having one or more functional diamine group(s) that contain a primary amine group, and which may be linked terminally, laterally or both terminally and laterally as desired via an alkylene linkage to silicon are well known and are available commercially, for example from Dow Corning, General Electric and Shin-Etsu. Exemplary suitable functional diamine silicone fluids are silicone fluids having one or more aminoalkylaminoalkylene functional groups include, for example, aminoethylaminopropyl functional silicone fluids such as KF 393 from Shin-Etsu and aminoethylaminoisobutyl functional silicone fluids such as X2-8107 and Q2-8220 from Dow Corning. While the equivalent weight of the silicone fluids or compositions which may be employed in the preparation of the pyrrolidone-containing carboxyl functional polysiloxanes of the present invention is not critical, and suitable compositions may have equivalent weights of 15,000 or even higher, although silicone fluids having equivalent weights from about 500 to about 12,000 are in general preferred.
As indicated, the pyrrolidone-containing carboxyl functional polysiloxane compositions including the amphoteric class of polysiloxanes of the present invention are readily prepared by reaction of diamino functional silicone fluids wherein each of the diamine groups must contain a primary amine with itaconic acid or its ester. The organosilicone compositions are substantially compatible with the itaconic acid or ester derivative thereof and forms a homogeneous reaction mixture therewith. Itaconic acid (methylene succinic acid) is a compound of the formula:
CH2xe2x95x90C(COOR9)CH2COOR9
wherein R9, which can be the same or different, is hydrogen or lower alkyl (1-6 carbon atoms).
The compound itaconic acid is available commercially from Rhone Poulenc and Pfizer Chemicals Division whereas ester derivatives thereof are available from Morflex Inc., Greensboro, N.C. The compounds are produced by known fermentation techniques although chemical synthesis methods are also known.
In another aspect of the present invention, there are provided novel silicone-containing amidoamine compositions that are suitable for use as surfactants and a variety of other applications as well as intermediate reactants preferably for use in the preparation of derivatives of the novel pyrrolidone-containing functional carboxyl polysiloxane compositions of the invention as hereinabove described. The novel amidoamine compositions of the invention may be represented by the general formula: 
wherein: R10 is a silicone backbone chain as herein described to which at least one pyrrolidone-containing carboxyl functional group or amidoamine derivative thereof is attached as hereinabove shown;
R6 is hydrogen or alkyl, hydroxyalkyl or alkenyl up to 6 carbon atoms each, cycloalkyl of up to 6 carbon atoms or polyoxyalkylene of up to 10 carbon atoms, preferably from 2 to 5 carbon atoms, within the oxyalkylene unit and at least one R6 is hydrogen;
R7 and R8, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl, and polyoxyalkylene of up to 10 carbon atoms; in addition R7 and R8 taken together with the nitrogen to which they are attached may represent N-heterocycle;
F1 is linear or branched alkylene of 1-12 carbon atoms, preferably methylene, propylene and isobutylene;
F is linear or branched alkylene of 1-10 carbon atoms, preferably ethylene and isopropylene;
B is xe2x80x94NR9 wherein R9 is hydrogen or lower alkyl (C1-6) and further wherein n2 is 0 or 1;
n3 is an integer and is at least 1, preferably an integer from 2 to 12; and
d is an integer from 1 or greater, generally from 1-50 and preferably 2-10.
The novel silicone-containing amidoamine compositions of the invention can be prepared as follows: 
wherein: R10 is a silicone backbone chain as herein described to which at least one pyrrolidone-containing carboxyl functional group or amidoamine derivative thereof is attached as hereinabove shown;
R5 is hydrogen, lower alkyl (C1-6) or alkali metal;
R6 is hydrogen or alkyl, hydroxyalkyl or alkenyl up to 6 carbon atoms each, cycloalkyl of up to 6 carbon atoms or polyoxyalkylene of up to 10 carbon atoms, preferably from 2 to 5 carbon atoms, within the oxyalkylene unit and at least one R6 is hydrogen;
R7 and R8, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl, and polyoxyalkylene of up to 10 carbon atoms; in addition R7 and R8 taken together with the nitrogen to which they are attached may represent an N-heterocycle;
F1 is linear or branched alkylene of 1-12 carbon atoms;
F is linear or branched alkylene of 1-10 carbon atoms;
B is xe2x80x94NR9, wherein R9 is hydrogen or lower alkyl and further wherein n2 is 0 or 1;
n3 is an integer and is at least 1, preferably an integer from 2 to 12;
d and D is an integer from 1 or greater, generally from 1-50 and preferably 2-10. The reactant ratio of the amine reactant to the carboxyl reactant on the silicon is preferably 1:1 but can be varied in ratio from 1:0.8 to 1:1.2.
Silicone-containing amidoamines of the invention are readily prepared by the above coupling reaction from the novel polysiloxane compositions of the present invention having one or more pyrrolidone-containing functional carboxyl group(s) as hereinabove described.
The above coupling reaction for preparing the silicone-containing amidoamine compositions can be carried out neat or can be carried out in an inert solvent such as xylene, toluene, chlorobenzene or the like. While the equivalent weight of the silicone-containing amidoamine compositions is not critical, preferably the equivalent weight of such compositions will range from about 500 to 15,000.
The novel pyrrolidone-containing carboxyl functional polysiloxane compositions including the amphoteric class of polysiloxanes and the amidoamine derivatives thereof display many of the well known properties of silicone such as emolliency, detackification, smoothing, lubrication and sufactancy properties while, in addition, making them suitable as precursor reactors for the preparation of a variety of silicone-containing derivatives. In this connection, the novel compositions of the invention are suitable for the preparation of silicone-containing compositions which exhibit the unique property of water-dispersibility or solubility and substantivity.
It is therefore a further aspect of the invention to use the novel compositions of the invention, for example, in cosmetic and the like personal care preparations, especially in preparations for skin treatment and hair care. In this connection, personal care formulations can be hair conditioners and skin-treatment cremes and lotions. Other formulations where the unique properties of the novel compositions of the invention can be utilized include make-up cremes, sunscreens, lipstick, pressed powders, skin-toners, deodorants, antiperspirants and the like. Personal care preparations to which the novel compositions of the inventions have been added in amounts of at least 0.1%, preferably from 0.1% to 10%, by weight, and can contain other additives, provide skin treating products with non-irritating, non-greasy film on the skin that does not evaporate and therefore provides long lasting protection. In addition, these novel compositions demonstrate useful hair xe2x80x9cdressingxe2x80x9d characteristics.
Among other advantages of the novel carboxyl functional polysiloxanes of the invention are their usefulness as paper and textile sizing and lubricating agents; treating agents for fillers, paper and plastics; anticorrosion agents for metal products, and the like.
The preparation of specific compositions of the invention is illustrated by the following specific examples which are provided herein for purposes of illustration only and are not intended to limit the scope therein.